[0001] This invention relates to a method of producing a high density silicon nitride sintered
body containing an oxide of yttrium and/or aluminum as a sintering aid.
[0002] Heretofore, there have been proposed various methods of producing high density silicon
nitride sintered bodies. As a typical method, there is known a method wherein silicon
nitride powder is added to a sintering aid and an organic binder, shaped by a press
molding or the like, covered with glass and then subjected to a hot isostatic pressing
from Japanese Patent Application Publication No. 59-35,870.
[0003] In the hot isostatic pressing method using a glass capsule as mentioned above, high
density silicon nitride sintered bodies can be obtained in many cases, but when an
oxide of yttrium and/or aluminum is used as a sintering aid, it becomes clear that
the desired high densification cannot be achieved. That is, in the latter system,
relatively large pores unfavorably remain in the sintered body after the hot isostatic
pressing.
[0004] It is, therefore, an object of the invention to solve the aforementioned problem
and to provide a method capable of producing high density silicon nitride sintered
bodies in the system containing the oxide of yttrium and/or aluminum as a sintering
aid.
[0005] According to the invention, there is the provision of a method of producing a high
density silicon nitride sintered body, comprising shaping a mixture of silicon nitride
powder containing not less than 90% of α-phase and at least an oxide of yttrium and/or
aluminum as a sintering aid, preliminarily sintering the resulting shaped body to
obtain a presintered body having an adjusted β-phase forming ratio of silicon nitride
of 20∼60%, and then covering the presintered body with glass to conduct hot isostatic
pressing.
[0006] The invention will be described with reference to the accompanying drawing, wherein:
Fig. 1 is a flow chart showing an embodiment of practicing the method according to
the invention.
[0007] In the invention, the shaped body is preliminarily sintered so as to adjust the
β-phase forming ratio of α-type silicon nitride to 20 ∼ 60% before the hot isostatic
pressing (hereinafter abbreviated as HIP) with the glass capsule, whereby high density
silicon nitride sintered bodies can be obtained even in the system containing the
oxide of yttrium and/or aluminum as a sintering aid. The reason why the β-phase forming
ratio is limited to 20 ∼ 60% is due to the fact that when the β-phase forming ratio
is outside the above range, the maximum pore size remaining in the sintered body becomes
larger and the densification is insufficient as seen from the following examples.
[0008] Moreover, the β-phase forming ratio defined in the invention is determined by the
following equation:
β-phase forming ratio (%) = (β2 - β1/α + β1) × 100
wherein α is an α-phase quantity before the preliminary sintering, β1 is a β-phase
quantity before the preliminary sintering and β2 is a β-phase quantity after the
preliminary sintering.
[0009] The reason why the high density silicon nitride sintered body is obtained by limiting
the β-phase forming ratio to a value lower than the conventional value before the
HIP treatment with the glass capsule is considered due to the following. That is,
the pores are existent in the silicon nitride sintered body, and needle crystal of
β-type silicon nitride usually protrudes toward the inside of the pore. In this case,
the needle crystal has substantially no defect and is approximately equal to the theoretical
strength. Thus, in a structure in which the needle crystals of β-type silicon nitride
extend towards the inside of the pores in the silicon nitride sintered body, i.e.
a bridge structure, the pores cannot be broken even when external force is applied.
Therefore, the pores included in the sintered body cannot be broken even when the
high β-type silicon nitride sintered body is subjected to the HIP treatment.
[0010] An embodiment of the method according to the invention is shown by a flow chart in
Fig. 1. At first, silicon nitride powder containing not less than 90% of α-phase with
a given particle size is mixed with a sintering aid such as Y₂O₃ and/or Al₂O₃ and
an organic binder such as polyvinyl alcohol or the like, and then pressed in a mold
to form a shaped body. Next, the shaped body is preliminarily sintered at 1200 ∼ 2000°C
in an atmosphere of N₂ gas for 0.5∼2 hours to adjust the β-phase forming ratio. The
desirable β-phase forming ratio can be attained by changing the presintering temperature,
the particle size of the starting material, and the kind and amount of the sintering
aid. Finally, the preliminarily sintered body is covered with glass and then subjected
to hot isostatic pressing, whereby the desirable high density silicon nitride sintered
bodies are obtained.
[0011] The following examples are given in illustration of the invention and are not intended
as limitations thereof.
Example
[0012] A starting powder of silicon nitride having an average particle size of 0.8 µm and
containing not less than 90% of α-phase was mixed with Y₂O₃ and Al₂O₃ as a sintering
aid in a mixing ratio as shown in the following Table 1 and then pressed in a mold
into a size of 60×60×10 mm under a given pressure. This shaped body was preliminarily
sintered in an N₂ gas atmosphere of an atmospheric pressure under conditions as shown
in Table 1. After the preliminary sintering, the resulting presintered body was enveloped
with a glass capsule and then subjected to hot isostatic pressing under conditions
as shown in Table 1 to obtain sintered bodies of acceptable examples and comparative
examples.
[0013] In each sample of the acceptable examples, and comparative examples, an area of 3×3
mm was polished into mirror state and observed by means of an optical microscope of
400 magnification to measure a maximum pore size. Moreover, the density of the sintered
body in all of the acceptable examples and comparative examples was not less than
99% of theoretical. Further, the β-phase forming ratio after the preliminary sintering
was measured with respect to the acceptable examples and comparative examples. The
measured results are also shown in Table 1.
Table 1
Run No. |
Sintering aid (wt%) |
Preliminary sintering conditions (°C × hr) |
β-phase forming ratio in preliminarily sintered body (%) |
HIP conditions with glass capsule (°C × MPa) × 1hr |
Maximum pore size in sintered body (µm) |
Remarks |
|
Y₂O₃ |
Al₂O₃ |
total |
|
|
|
|
|
1 |
2.5 |
0 |
2.5 |
1700 × 1 |
20 |
1800 × 200 |
2.5 |
Acceptable Example |
2 |
0 |
2.5 |
2.5 |
1650 × 1 |
35 |
1800 × 200 |
2.0 |
3 |
2.5 |
2.5 |
5.0 |
1500 × 1 |
60 |
1700 × 200 |
1.5 |
4 |
1.0 |
6.0 |
7.0 |
1400 × 2 |
30 |
1700 × 200 |
0.5 |
5 |
6.0 |
6.0 |
12.0 |
1400 × 1 |
45 |
1700 × 50 |
1.0 |
6 |
0 |
12.0 |
12.0 |
1200 × 3 |
35 |
1700 × 50 |
2.0 |
7 |
7.0 |
5.0 |
12.0 |
1700 × 1 |
75 |
1700 × 50 |
7.0 |
Comparative Example |
8 |
0 |
12.0 |
12.0 |
1500 × 1 |
65 |
1700 × 200 |
6.0 |
9 |
1.0 |
6.0 |
7.0 |
1600 × 2 |
65 |
1700 × 200 |
6.5 |
10 |
2.5 |
2.5 |
5.0 |
1200 × 3 |
15 |
1800 × 200 |
7.0 |
[0014] As seen from the results of Table 1, the maximum pore size in the sintered body in
the acceptable examples according to the invention is smaller than those of the comparative
examples
from which it is apparent that the sintered body according to the invention is highly
densified at a more preferable state.
[0015] The invention is not intended to only the above example, and various changes and
modifications are made possible. For instance, in the above example, only Y₂O₃ and/or
Al₂O₃ are added as a sintering aid, but another sintering aid may be further added
to obtain the same result.
[0016] As mentioned above, according to the method of the invention, the shaped body is
preliminarily sintered before the HIP treatment with the glass capsule, so that high
density silicon nitride sintered bodies can be obtained without the influence of needle-like
β-type silicon nitride.
1. A method of producing a high density silicon nitride sintered body, comprising
shaping a mixture of silicon nitride powder containing not less than 90% of α-phase
and at least an oxide of yttrium and/or aluminum as a sintering aid, preliminarily
sintering the resulting shaped body to obtain a presintered body having an adjusted
β-phase forming ratio of silicon nitride of 20∼60%, and then covering the presintered
body with glass to conduct hot isostatic pressing.
2. The method according to claim 1, wherein said sintering aid is Y₂O₃ and/or Al₂O₃.